EP0846657B1 - Synthèse du pentafluorure de phosphore par fluoration du trichlorure de phosphore - Google Patents
Synthèse du pentafluorure de phosphore par fluoration du trichlorure de phosphore Download PDFInfo
- Publication number
- EP0846657B1 EP0846657B1 EP97402857A EP97402857A EP0846657B1 EP 0846657 B1 EP0846657 B1 EP 0846657B1 EP 97402857 A EP97402857 A EP 97402857A EP 97402857 A EP97402857 A EP 97402857A EP 0846657 B1 EP0846657 B1 EP 0846657B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reactor
- pcl
- pressure
- phosphorus
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Revoked
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/10—Halides or oxyhalides of phosphorus
Definitions
- the subject of the present invention is the manufacture in the liquid phase of phosphorus pentafloride by fluorination of phosphorus trichloride with anhydrous hydrogen fluoride (HF) in the presence of chlorine.
- HF hydrous hydrogen fluoride
- Phosphorus pentafloride gaseous at room temperature, is used by the electronics industry, intervenes as a fluorinating agent in various chemical reactions but above all serves as a raw material for the manufacture of lithium hexafluorophosphate (LiPF 6 ) whose main industrial application concerns electrolytes from rechargeable lithium-ion batteries, the industrial development of which is promising.
- the process according to the invention is characterized by easy implementation since it takes place in the liquid phase, the runaway of which is more easily controlled than processes using solids and gases, and because it uses usual reagents in the chemistry of fluorinated compounds and finally by a maximum conversion rate to PF 5 ; this process is characterized in that it comprises the fluorination of phosphorus trichloride with anhydrous hydrogen fluoride in the liquid phase in the presence of chlorine and in that the molar ratio Cl 2 / PCl 3 is between 1 and 1.2 .
- anhydrous HF is meant hydrogen fluoride containing less than 100 ppm of water but the process according to the invention can also use HF containing up to 500 ppm of water.
- the method according to the invention can be implemented discontinuously, but it is advantageously carried out continuously.
- the HF / PCl 3 molar ratio is at least equal to 5 and preferably between 6 and 30.
- the introduction of chlorine into the reaction apparatus operating in continuous or discontinuous mode can be carried out either in the liquid state under pressure sufficient (typically 1 MPa at room temperature), or in the gaseous state. In in the latter case, it dissolves as soon as it comes into contact with the reaction mass.
- the reaction can be carried out, but it is not necessary, in the presence of fluorination catalyst (s) among which mention may be made of Lewis acids and / or strong organic acids, halides, oxides and oxyhalides of the elements of the groups IVa and b, Va and b Vla and b and VIII.
- fluorination catalyst among which mention may be made of Lewis acids and / or strong organic acids, halides, oxides and oxyhalides of the elements of the groups IVa and b, Va and b Vla and b and VIII.
- fluorination catalyst among which mention may be made of Lewis acids and / or strong organic acids, halides, oxides and oxyhalides of the elements of the groups IVa and b, Va and b Vla and b and VIII.
- paratoluenesulfonic, trifluoroacetic and triflic acids chlorides and fluorides such as FeCl 3 , AlCl 3 , SbF 3 , TiF 4 , SnF 4
- the reaction can be carried out in a conventional apparatus, well known to those skilled in the art. It can be a reactor equipped with a stirring system, a thermometric probe and fitted with closure means made of material capable of withstanding pressure and low temperatures; the material can for example be chosen from ordinary steels or stainless, alloys and in particular based on chromium / nickel / iron / copper such than those marketed under the names INCONEL®, MONEL® and HASTELLOY® C.
- the reactants into the reactor at a temperature much lower than room temperature, preferably less than or equal to -30 ° C. It is also preferred to introduce the reagents separately, preferably respecting the following order: PCl 3 then HF and finally Cl 2 .
- reaction mixture is then placed under stirring as soon as the mixture liquefies, stirring being maintained until the maximum pressure and the room temperature are reached.
- the contents of the reactor are decompressed and the products formed and / or those are separated. having not reacted.
- the decompression can be carried out using a second reactor - in which one can for example carry out the synthesis of LiPF 6 - or even using absorbers which have the role of absorbing the reaction gases in a appropriate solvent from which all traces of water may have been eliminated beforehand, which can cause hydrolysis of PF 5 .
- solvent for the absorbers mention will be made of anhydrous acetonitrile.
- the reaction is carried out in conventional apparatus, well known to those skilled in the art. It can be a reactor fed in gaseous and / or liquid form, with raw materials and recycling, and heated or cooled adequately. It must promote contact between the reagents by means of a suitable geometry, method of introducing the reagents and a mixing technique.
- the liquid phase at the bottom of the reactor can be mainly composed of liquid HF, but it can equally advantageously be mainly composed of liquid PCl 3 . According to another variant, it is possible to operate in the liquid HCl phase.
- the reactor can be equipped with a condenser allowing in particular to adjust the HF concentration.
- the pressure under which the process according to the invention is carried out is not critical in itself, since it allows the reaction to be carried out in phase liquid, i.e. it is sufficient to maintain the reagents present in the reactor, essentially in liquid form. It varies depending on the temperature and the composition of the reaction medium.
- the pressure of the reaction system is generally chosen between 0.5 and 10 MPa and preferably the reaction is carried out at constant pressure, the reactor being advantageously provided with a appropriate pressure regulation.
- the process according to the invention can be carried out in a wide range of temperatures generally between - 40 and 100 ° C, but we prefer to operate at around room temperature.
- the gases from the reaction gaseous and possibly liquid, are treated in a conventional manner to separate PF 5 from the other products resulting from the reaction.
- the crude gaseous effluent from the reaction consisting essentially of PF 5 , HCl, possibly Cl 2 in low concentration if an excess of chlorine has been used relative to the amount of PCl 3 introduced, and HF entrained, can for example be absorbed in a solution of LiF in HF to obtain a solution of LiPF 6 in HF.
- the solution of LiPF 6 in HF can then be treated according to techniques known to those skilled in the art.
- the DEWAR is removed and the reactor with stirring in an enclosure maintained at room temperature.
- the pressure inside the reactor is measured, which reaches 2 MPa after 60 min then stabilizes between 2.1 and 2.2 MPa between 60 and 108 min.
- the temperature of the liquid phase reaches + 22 ° C and stabilizes at this value.
- the mixture is heated reactor up to 100 ° C, the pressure then reaching 4 MPa, then cooled to 22 ° C. It is then found that the pressure is identical to that before the step of heating which indicates that no further reaction has occurred within the reactor during the heating / cooling cycle.
- the reactor contents are then slowly decompressed using 2 serial washers filled with 194 g for the first and 196 g for the second anhydrous acetonitrile (dehydrated for 24 h on 3 ⁇ molecular sieve).
- the gases which are not absorbed in the 2 absorbers pass through a dryer made up of calcium chloride, then are absorbed first in water (8.9 g) then in a sodium hydroxide-sodium mixture, intended to measure the chlorine content. of this gas flow; it is known to those skilled in the art that in a sufficient excess of water, PF 5 is transformed quantitatively into HF and H 3 PO 4 .
- the liquid temperature After 100 min of agitation of the reactor once the DEWAR vessel has been removed, the liquid temperature reaches 15 ° C and pressure 2.8 MPa. After a period about 450 min, the temperature stabilizes at 21 ° C and the pressure at 3.5 MPa.
- a second reactor identical to the first is charged with 14.3 g of fluoride lithium (LiF) and 388 g of anhydrous liquid HF under a helium pressure of 0.3 MPa.
- the gases from the first reactor are then transferred by absorption in the second reactor; the decompression of the first reactor due to the transfer of gas in the second reactor takes place in 6 h and its pressure decreases from 3.5 to 0.5 MPa.
- a water washer At the outlet of the second reactor, there is in series a water washer and a sodium hydroxide-sulfite washer in which the chlorides, fluorides and phosphorus ions are measured.
- the second reactor is then decompressed through a series of 3 washers, the first and the last are water washers while the intermediate washer is a sodium hydroxide-sodium washer, and 67 g of LiPF 6 .
- the contents of reactors 1 and 2 are slightly heated to atmospheric pressure on the one hand to eliminate and transfer the content of the first reactor into the second, on the other hand to evaporate the excess HF in the second reactor.
- the yield of the reaction in PF 5 is quantitative (formation of 3,000 mmol of HCI and 3,000 / 5 mmol of PF 5 )
- Example 2 The operating conditions of Example 2 are repeated, but operating with a lower excess of HF, ie 4,200 mmol of HF for 600 mmol of PCl 3 and 750 mmol of Cl 2 .
- the assays carried out from the effluents of the washers show a total conversion of PCl 3 to PF 5 in 450 min.
- a reaction temperature close to 40 ° C. is maintained.
- the steady state that is to say when the pressure within the reactor reaches 1.5 MPa, and after 8 h of continuous operation under the above conditions, the crude mixture N is continuously withdrawn 2 , PF 5 , HCl, Cl 2 and HF at the top of the condenser which ensures the recondensation of untrained and vaporized HF given the exothermicity of the reaction.
- the effluents withdrawn are sent to absorbers in series, the content of which after absorption is measured and which care is taken to regularly replace the absorbent liquid in order to avoid saturation.
- reaction yield is total and its productivity (reduced to the useful volume of the reactor, ie 500 ml) is 250 g of PF 5 / h * I.
- the temperature in the reactor is 70 ° C and that of the gas leaving the condenser is 0 ° C.
- the gases at the outlet are trapped during a given period of time in 2 absorbers in series (soda and soda / sulfite) for which one doses P, Cl - , F - on the one hand and Cl - on the other hand (Cl 2 being reduced to Cl - ).
- the reaction mass is maintained at around 64 ° C and that of the gases effluents at 0 ° C.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Description
- la fluoration du phosphore par le fluor (GROS, HAYMAN et STUART Trans. Faraday Soc. (1966), 62(10), 2716-18) ou par ClF3 en milieu HF liquide (CLIFFORD BEACHELL et JACK J. lnorg. Nucl. Chem. (1957), 5, 57-70), toutes deux peu industrialisables étant donné la violence des réactions,
- la réaction de spath fluor sur l'acide phosphorique en présence de trioxyde de soufre (FR 2.086.784) dont le rendement n'atteint que 12 %,
- la fluoration du fluorure de phosphoryle (POF3) par le fluorure d'hydrogène en présence de trioxyde de soufre (FR 2.082.502) dont les principaux inconvénients sont un rendement médiocre et la formation d'acide sulfurique, très corrosif en présence de HF,
- la fluoration du pentachlorure de phosphore (PCl5) par le trifluorure d'arsenic (RUFF Die Chemie des Fluors (1929), 239) ou par le fluorure de calcium (DD290 889), par HF en phase liquide et/ou gazeuse (J60-251.109, J04-175.216, J06-056.413) ; mais la manipulation de PCl5, solide très hygroscopique, est particulièrement délicate.
- PCl3 :
- 27,5 g (200 mmoles)
- HF :
- 80,4 g (4.020 mmoles)
- Cl2 :
- 19 g (268 mmoles).
- CI- :
- 2.923 mmoles dans le laveur 1
67 mmoles dans le laveur 3
10 mmoles dans le laveur 5 - Cl2 :
- 178 mmoles dans le laveur 2
- F- :
- 6.089 mmoles dans le laveur 1
20.083 mmoles dans le laveur 3
2.920 mmoles dans le laveur 5 - P :
- 87 mmoles dans le laveur 1
136 mmoles dans le laveur 3
3 mmoles dans le laveur 5
- PF5 :
- 4 M/h
- HF :
- 0,03 M/h
- HCI :
- 2,5 M/h
- Cl2 :
- 0,05 M/h
- PCl3 :
- 4 M/h
- HF :
- 20,8 M/h
- Cl2 :
- 4,8 M/h
- PF5 :
- 4 M/h
- HF :
- 0,8 M/h
- HCI :
- 20 M/h
- Cl2 :
- 0,8 M/h
Claims (5)
- Procédé de préparation du pentafluorure de phosphore, caractérisé en ce qu'on opère en phase liquide par fluoration du trichlorure de phosphore avec de l'acide fluorhydrique anhydre en présence de chlore et en ce que le rapport molaire Cl2/PCl3 est compris entre 1 et 1,2.
- Procédé selon la revendication 1, caractérisé en ce que le rapport molaire HF/PCl3 est au moins égal à 5 et de préférence compris entre 6 et 30.
- Procédé selon la revendication 1 ou 2, caractérisé en ce qu'il est mis en oeuvre de manière discontinue.
- Procédé selon la revendication 3, caractérisé en ce qu'on introduit les réactifs au sein du réacteur à basse température, de préférence séparément et dans l'ordre suivant PCl3 puis HF et enfin Cl2, puis agite le mélange réactionnel jusqu'à ce que la pression soit constante puis décomprime lentement le réacteur et sépare les produits formés.
- Procédé selon la revendication 1 ou 2, caractérisé en ce qu'il est mis en oeuvre de manière continue à une température comprise entre - 40 et 100 °C, et de préférence voisine de la température ambiante à une pression comprise entre 0,5 et 10 MPa et de préférence à pression constante.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9614808 | 1996-12-03 | ||
FR9614808A FR2756553B1 (fr) | 1996-12-03 | 1996-12-03 | Synthese du pentafluorure de phosphore par fluoration du trichlorure de phosphore |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0846657A1 EP0846657A1 (fr) | 1998-06-10 |
EP0846657B1 true EP0846657B1 (fr) | 2000-08-16 |
Family
ID=9498273
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP97402857A Revoked EP0846657B1 (fr) | 1996-12-03 | 1997-11-27 | Synthèse du pentafluorure de phosphore par fluoration du trichlorure de phosphore |
Country Status (7)
Country | Link |
---|---|
EP (1) | EP0846657B1 (fr) |
JP (1) | JPH10245211A (fr) |
KR (1) | KR19980063750A (fr) |
AT (1) | ATE195494T1 (fr) |
CA (1) | CA2223658A1 (fr) |
DE (1) | DE69702827D1 (fr) |
FR (1) | FR2756553B1 (fr) |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2781474B1 (fr) * | 1998-07-07 | 2000-09-08 | Atochem Elf Sa | PROCEDE INDUSTRIEL DE FABRICATION EN CONTINU D'UN MELANGE PF5 ET D'HCl ET MELANGE AINSI OBTENU |
JP5307409B2 (ja) | 2007-08-16 | 2013-10-02 | ステラケミファ株式会社 | 五フッ化リン及び六フッ化リン酸塩の製造方法 |
JP5341425B2 (ja) * | 2008-08-08 | 2013-11-13 | ステラケミファ株式会社 | フッ化物ガスの製造方法 |
JP2010042937A (ja) * | 2008-08-08 | 2010-02-25 | Stella Chemifa Corp | 五フッ化リン及び六フッ化リン酸塩の製造方法 |
JP4983972B2 (ja) * | 2010-10-14 | 2012-07-25 | ダイキン工業株式会社 | 五フッ化リンの製造方法 |
JP5803098B2 (ja) * | 2010-12-17 | 2015-11-04 | ダイキン工業株式会社 | 五フッ化リンの製造方法 |
KR101395860B1 (ko) * | 2011-07-13 | 2014-05-16 | 솔브레인 주식회사 | 육불화인산리튬의 제조방법 |
CN102320584B (zh) * | 2011-10-26 | 2012-10-10 | 核工业理化工程研究院华核新技术开发公司 | 制备五氟化磷的方法 |
JP5865314B2 (ja) * | 2013-08-21 | 2016-02-17 | ステラケミファ株式会社 | 五フッ化リン及び六フッ化リン酸塩の製造方法 |
CN110072807B (zh) * | 2017-03-13 | 2023-05-23 | 关东电化工业株式会社 | 五氟化磷的制造方法 |
CN112678850A (zh) * | 2020-12-30 | 2021-04-20 | 徐兴碧 | 一种六氟磷酸锂的生产装置及方法 |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0816287A1 (fr) * | 1996-06-26 | 1998-01-07 | Solvay Fluor und Derivate GmbH | Préparation de pentafluorure inorganique |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2987713B2 (ja) * | 1990-11-09 | 1999-12-06 | 株式会社トーケムプロダクツ | 高純度六フツ化リン酸化合物の製造方法 |
JP3204415B2 (ja) * | 1992-08-10 | 2001-09-04 | セントラル硝子株式会社 | 六フッ化リン酸塩の製造方法 |
-
1996
- 1996-12-03 FR FR9614808A patent/FR2756553B1/fr not_active Expired - Fee Related
-
1997
- 1997-11-27 EP EP97402857A patent/EP0846657B1/fr not_active Revoked
- 1997-11-27 DE DE69702827T patent/DE69702827D1/de not_active Expired - Lifetime
- 1997-11-27 AT AT97402857T patent/ATE195494T1/de not_active IP Right Cessation
- 1997-12-03 JP JP9348595A patent/JPH10245211A/ja not_active Withdrawn
- 1997-12-03 KR KR1019970065608A patent/KR19980063750A/ko not_active Application Discontinuation
- 1997-12-03 CA CA002223658A patent/CA2223658A1/fr not_active Abandoned
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0816287A1 (fr) * | 1996-06-26 | 1998-01-07 | Solvay Fluor und Derivate GmbH | Préparation de pentafluorure inorganique |
Also Published As
Publication number | Publication date |
---|---|
JPH10245211A (ja) | 1998-09-14 |
KR19980063750A (ko) | 1998-10-07 |
EP0846657A1 (fr) | 1998-06-10 |
DE69702827D1 (de) | 2000-09-21 |
ATE195494T1 (de) | 2000-09-15 |
FR2756553B1 (fr) | 1999-01-22 |
CA2223658A1 (fr) | 1998-06-03 |
FR2756553A1 (fr) | 1998-06-05 |
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